Maghemite

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Maghemite
General
CategoryOxide minerals
Formula
(repeating unit)
γ-Fe2O3
IMA symbolMgh[1]
Strunz classification4.BB.15
Crystal systemCubic with a tetragonal supercell
Crystal classGyroidal (432)
(same H-M symbol)
Space groupP4132, P4332
Unit cella = 8.33 Å; Z = 8 or a = 8.35 Å c = 24.99 Å; Z = 8 for tetragonal supercell
Identification
ColorBrown, bluish black; brown to yellow in transmitted light; white to bluish gray in reflected light.
Crystal habitRarely as minute octahedral crystals, or acicular overgrowths; commonly as coatings on or replacements of magnetite; massive.
CleavageNone
FractureSubconchoidal
Mohs scale hardness5
LusterDull
StreakBrown
DiaphaneityOpaque, transparent in thin fragments
Specific gravity4.860 (calculated)
Optical propertiesIsotropic
Other characteristicsStrongly magnetic
References[2][3][4][5]

Maghemite (Fe2O3, γ-Fe2O3) is a member of the family of iron oxides. It has the same formula as hematite, but the same spinel ferrite structure as magnetite (Fe3O4) and is also ferrimagnetic. It is sometimes spelled as "maghaemite".

Maghemite can be considered as an Fe(II)-deficient magnetite with formula [6] where represents a vacancy, A indicates tetrahedral and B octahedral positioning.

Occurrence[edit]

Maghemite forms by weathering or low-temperature oxidation of spinels containing iron(II) such as magnetite or titanomagnetite. Maghemite can also form through dehydration and transformation of certain iron oxyhydroxide minerals, such as lepidocrocite and ferrihydrite. It occurs as widespread brown or yellow pigment in terrestrial sediments and soils. It is associated with magnetite, ilmenite, anatase, pyrite, marcasite, lepidocrocite and goethite.[3] It is known to also form in areas that have been subjected to bushfires (particularly in the Leonora area of Western Australia) magnetising iron minerals.

Maghemite was named in 1927 for an occurrence at the Iron Mountain Mine, northwest of Redding, Shasta County, California.[5] The name alludes to somewhat intermediate character between magnetite and hematite. It can appear blue with a grey shade, white, or brown.[7] It has isometric crystals.[4] Maghemite is formed by the topotactic oxidation of magnetite.

Cation distribution[edit]

There is experimental[8] and theoretical[9] evidence that Fe(III) cations and vacancies tend to be ordered in the octahedral sites, in a way that maximizes the homogeneity of the distribution and therefore minimizes the electrostatic energy of the crystal.

Electronic structure[edit]

Maghemite is a semiconductor with a bandgap of ca. 2 eV,[10] although the precise value of the gap depends on the electron spin.[9]

Applications[edit]

Maghemite exhibits ferrimagnetic ordering with a high Néel temperature (~950 K), which together with its low cost and chemical stability led to its wide application as a magnetic pigment in electronic recording media since the 1940s.[11]

Maghemite nanoparticles are used in biomedicine, because they are biocompatible and non-toxic to humans, while their magnetism allows remote manipulation with external fields.[12]

As pollutant[edit]

It was found in 2022 that high levels of maghemite particles small enough to enter the bloodstream if inhaled, some as small as five nanometres, were present in the London Underground transport system. The presence of the particles indicated that they are suspended for long periods due to poor ventilation, particularly on platforms. The health implications presented by the particles were not investigated.[13][14]

References[edit]

  1. ^ Warr, L.N. (2021). "IMA–CNMNC approved mineral symbols". Mineralogical Magazine. 85 (3): 291–320. Bibcode:2021MinM...85..291W. doi:10.1180/mgm.2021.43. S2CID 235729616.
  2. ^ Mineralienatlas
  3. ^ a b Anthony, John W.; Bideaux, Richard A.; Bladh, Kenneth W.; Nichols, Monte C., eds. (1997). "Maghemite" (PDF). Handbook of Mineralogy. Vol. III (Halides, Hydroxides, Oxides). Chantilly, VA, US: Mineralogical Society of America. ISBN 0962209732.
  4. ^ a b Maghemite. Mindat
  5. ^ a b Maghemite. Webmineral
  6. ^ Cornell, R. M. and Schwertmann, Udo (2003) The Iron Oxides: Structure, Properties, Reactions, Occurrences and Uses. Wiley-VCH. p. 32. ISBN 3527302743.
  7. ^ Gaines, Richard V.; Skinner, H. Catherine W.; Foord, Eugene E.; Mason, Brian and Rosenzweig, Abraham (1997) Dana's new mineralogy, John Wiley & Sons. pp. 229-230. ISBN 0471193100.
  8. ^ Greaves, C. (1983). "A powder neutron diffraction investigation of vacancy ordering and covalence in γ-Fe2O3". J. Solid State Chem. 49 (3): 325–333. Bibcode:1983JSSCh..49..325G. doi:10.1016/S0022-4596(83)80010-3.
  9. ^ a b Grau-Crespo, Ricardo; Al-Baitai, Asmaa Y; Saadoune, Iman; De Leeuw, Nora H (2010). "Vacancy ordering and electronic structure of γ-Fe2O3 (maghemite): a theoretical investigation". Journal of Physics: Condensed Matter. 22 (25): 255401. arXiv:1005.2370. Bibcode:2010JPCM...22y5401G. doi:10.1088/0953-8984/22/25/255401. PMID 21393797. S2CID 778411.
  10. ^ Litter, M. I. & Blesa, M. A. (1992). "Photodissolution of iron oxides. IV. A comparative study on the photodissolution of hematite, magnetite, and maghemite in EDTA media". Can. J. Chem. 70 (9): 2502. doi:10.1139/v92-316.
  11. ^ Dronskowski, R. (2010). "The little maghemite story: A classic functional material". ChemInform. 32 (25): no. doi:10.1002/chin.200125209.
  12. ^ Pankhurst, Q A; Connolly, J; Jones, S K; Dobson, J (2003). "Applications of magnetic nanoparticles in biomedicine". Journal of Physics D: Applied Physics. 36 (13): R167. doi:10.1088/0022-3727/36/13/201. S2CID 51768859.
  13. ^ "Inhaled metal Tube dust can enter bloodstream, study finds". BBC News. 15 December 2022.
  14. ^ Sheikh, H. A.; Tung, P. Y.; Ringe, E.; Harrison, R. J. (2022-12-15). "Magnetic and microscopic investigation of airborne iron oxide nanoparticles in the London Underground". Scientific Reports. 12 (1): 20298. doi:10.1038/s41598-022-24679-4. ISSN 2045-2322. PMC 9755232. PMID 36522360.